CN111004536B - Antibacterial agent, preparation method thereof, coating, use method and application - Google Patents
Antibacterial agent, preparation method thereof, coating, use method and application Download PDFInfo
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- CN111004536B CN111004536B CN201911194626.XA CN201911194626A CN111004536B CN 111004536 B CN111004536 B CN 111004536B CN 201911194626 A CN201911194626 A CN 201911194626A CN 111004536 B CN111004536 B CN 111004536B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an antibacterial agent with lasting antibacterial performance, a preparation method thereof, a coating based on the antibacterial agent, and a using method and application of the coating. The antimicrobial agent comprises a composite nano silver material, wherein the composite nano silver material comprises a nano silver wire and magnetic particles loaded on the nano silver wire. The nano silver wire is a one-dimensional silver metal material with high length-diameter ratio, the length of the nano silver wire is in a micron size, and the diameter of the nano silver wire is in a nanometer size. After the silver nanowires and the magnetic metal particles are compounded, the silver nanowires and the magnetic metal particles can be directionally arranged in a certain direction under the action of a magnetic field, so that the silver nanowires can be embedded into the coating as a whole, the problem of insufficient antibacterial durability caused by the fact that common silver nanoparticles are easily dissolved out through pores with various sizes in the coating is solved, and the long-term stability of the antibacterial property is improved.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to an antibacterial agent, a preparation method thereof, a coating, a using method thereof and application thereof.
Background
The anticorrosion of the coating is an important means for the anticorrosion of steel, and along with the development of the industry and the improvement of the requirement on the environmental quality, the anticorrosion coating is developed from the protection function of single steel towards the directions of high performance, water-based environmental protection and multiple functions. The antimicrobial function of the coating is mostly achieved by adding suitable antimicrobial agents. Currently, the antibacterial agents for paints are mainly classified into natural antibacterial agents, organic antibacterial agents and inorganic antibacterial agents. The inorganic antibacterial agent is mainly a metal antibacterial agent, the principle lies in the sterilization or bacteriostasis capability of metals such as silver, copper, zinc, titanium and the like and ions thereof, compared with other antibacterial agents, the inorganic antibacterial agent has the characteristics of broad-spectrum antibiosis, high-efficiency sterilization, long effect, no drug resistance and the like, and can effectively make up the defects of natural and organic antibacterial agents.
The nano silver is a novel inorganic antibacterial agent commonly used in the current coating. The surface effect of the nano silver enables the antibacterial capacity of the nano silver to be more than 200 times of that of micron silver particles, and the antibacterial capacity of the nano silver is far greater than that of the traditional silver particle bactericides (such as silver nitrate and silver sulfadiazine). However, the nano silver is too small in size and is easily dissolved out through pores of various sizes in the coating, resulting in insufficient antibacterial durability of the coating. Researchers try to directly load nano silver on mesoporous graphene through an impregnation method, and the obtained composite material shows excellent catalytic antibacterial property. However, the impregnation method cannot ensure effective bonding between graphene and nano silver, and cannot ensure lasting catalytic antibacterial property. In addition, researches and records that the illite-montmorillonite clay/chitosan quaternary ammonium salt hybrid antibacterial agent selects illite-montmorillonite clay loaded organic antibacterial agent (chitosan quaternary ammonium salt) and inorganic antibacterial agent (silver nano particles) to improve the antibacterial effect, but the long-term stability of the illite-montmorillonite clay/chitosan quaternary ammonium salt hybrid antibacterial agent is still to be improved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an antibacterial agent with lasting antibacterial performance, a preparation method thereof, a coating based on the antibacterial agent, and a use method and application of the coating.
In a first aspect, one embodiment of the present invention provides an antimicrobial agent comprising a composite nanosilver material comprising nanosilver wires and magnetic particles supported on the nanosilver wires.
The antibacterial agent of the embodiment of the invention has at least the following beneficial effects:
the nano silver wire is a one-dimensional silver metal material with high length-diameter ratio, the length of the nano silver wire is in a micron size, and the diameter of the nano silver wire is in a nanometer size. When the nano silver wires and the magnetic metal particles are compounded, the nano silver wires and the magnetic metal particles can be directionally arranged in a certain direction under the action of a magnetic field, so that the nano silver wires and the magnetic metal particles can be integrally embedded into the coating, the problem of insufficient antibacterial durability caused by the fact that common nano silver particles are easily dissolved out through pores with various sizes in the coating is solved, and the long-term stability of the antibacterial property is improved.
According to other embodiments of the antimicrobial agent of the present invention, the magnetic particles may be particles of an optional metal capable of magnetic properties, such as particles of iron, cobalt, nickel, molybdenum, manganese, lanthanides, and the like.
According to other embodiments of the antimicrobial agent of the present invention, the magnetic particles are magnetic iron oxide (ferroferric oxide).
According to the antibacterial agent of other embodiments of the present invention, the diameter of the nano silver wire is 10 to 100nm, and the length of the nano silver wire is 5 to 80 μm.
In a second aspect, an embodiment of the present invention provides a method for preparing the antibacterial agent, wherein the method for preparing the antibacterial agent adopts a simple chemical coprecipitation method, and comprises the following steps:
(1) mixing the solution of the nano silver wires with the solution of the ferric salt;
(2) adjusting the pH value of the mixed solution to 11-12, and reacting;
wherein the iron salt comprises divalent iron ions and trivalent iron ions, and the molar ratio of the divalent iron ions to the trivalent iron ions is (1-1.5): 1.
according to other embodiments of the present invention, a method of preparing an antibacterial agent, the method comprising the steps of:
(1a)FeSO4·7H2o and FeCl3·6H2O is added into the mixture in a molar ratio (1-1.5): 1 preparing into a ferric salt water solution, and stirring and mixing uniformly;
(1b) and (3) mixing the aqueous solution of the nano silver wires according to the following formula (1-10): adding 100 parts by mass of the iron salt solution into the iron salt solution, and uniformly stirring and mixing the mixture;
(2) gradually dripping NaOH or KOH solution until the pH value of the mixed solution is 11-12, standing for 2-4h, washing with pure water after suction filtration, and drying in vacuum to obtain the composite nano silver material.
In a third aspect, an embodiment of the present invention provides a paint including the antibacterial agent described above.
The coating disclosed by the embodiment of the invention has at least the following beneficial effects:
the nano silver wire is a one-dimensional silver metal material with high length-diameter ratio, the length of the nano silver wire is in a micron size, and the diameter of the nano silver wire is in a nanometer size. After the nano silver wires and the magnetic metal particles are compounded, the nano silver wires and the magnetic metal particles can be directionally arranged in a certain direction under the action of a magnetic field, so that the nano silver wires and the magnetic metal particles can be integrally embedded into the coating, the problem of insufficient antibacterial durability caused by the fact that common nano silver particles are easily dissolved out through pores with various sizes in the coating is solved, and the antibacterial long-term stability of the coating is improved.
Coatings according to other embodiments of the present invention may be optional liquid phase coatings including, but not limited to, coatings such as polytetrafluoroethylene, fluorinated ethylene propylene copolymer, ceramic, and fluoropolymer resin coatings, or solid phase coatings including, but not limited to, coatings such as meltable polytetrafluoroethylene plastic, epoxy powder, polyester powder, and acrylate powder coatings, which are doped with an amount of an antimicrobial agent to increase their antimicrobial durability.
Coatings according to other embodiments of the invention further include silicates, zinc powder, anti-algae agents, and adjuvants.
The nano silver wire with high length-diameter ratio used as the antibacterial agent can form a high-efficiency conductive network with zinc powder in the coating, improve the cathode protection effect of the coating, reduce the addition of the zinc powder and prolong the anticorrosion life of the coating.
According to the paint of other embodiments of the invention, based on the total mass of the paint, the mass fraction of the silicate is 30-50 wt%, the mass fraction of the zinc powder is 40-69 wt%, the mass fraction of the antibacterial agent is 0.1-5 wt%, the mass fraction of the anti-algae agent is 0.1-2 wt%, and the mass fraction of the auxiliary agent is 0.1-3 wt%.
According to other embodiments of the coating, the silicate has a modulus of 4.5-7, and is a stable high modulus silicate. If the modulus of the silicate is too low, the active silicon hydroxyl is too little, the crosslinking density is low after a coating is formed, the water resistance is poor, and the adhesive force with a base material is poor; if the modulus of the silicate is too high, too many active hydroxyl groups are present, the zinc powder is crosslinked too quickly, the cohesion is too high, and the mechanical properties of the formed coating are reduced sharply.
According to other embodiments of the present invention, the silicate having a stable high modulus is obtained by reacting a silicate, a silane coupling agent and a silicone-acrylic emulsion.
According to other embodiments of the coating material of the present invention, the silane coupling agent includes, but is not limited to, at least one of KH-560, KH-602, and methyltriethoxysilane.
In other examples of the coating according to the invention, the zinc powder comprises a flaky zinc powder and a particulate zinc powder, the flaky zinc powder and the particulate zinc powder being present in a molar ratio of 1: (2-4). The anti-corrosion network formed by the flaky zinc powder and the granular zinc powder can prolong the shielding path of the coating to water and oxygen in the environment, simultaneously increase the release path of the antibacterial agent and the anti-algae agent, and improve the antibacterial and anti-algae performance of the coating.
According to the paint of other embodiments of the invention, the granular zinc powder is spherical, and the mesh number is 400-600 meshes; the thickness of the flaky zinc powder is 0.15-0.4 μm, the average grain diameter is 15-25 μm, and the ratio of the diameter to the thickness is 50-70.
According to other embodiments of the present invention, an anti-algae agent includes a porous support and an anti-algae compound supported on the porous support.
The composite anti-algae agent is formed by the anti-algae compound and the porous carrier, the fixing and slow release effects of the anti-algae agent are realized by utilizing the porous structure characteristic of the carrier, and the anti-algae property of the coating is prolonged while the corrosion-resistant life of the coating is prolonged.
According to other embodiments of the coating of the present invention, the porous carrier for the anti-algae agent may include, but is not limited to, at least one of diatomaceous earth, montmorillonite, zeolite, kaolin, bentonite, sepiolite, and the like.
According to other embodiments of the present invention, the anti-algae compound may include, but is not limited to, at least one of zinc pyrithione, cuprous oxide, methyl (RS) -2- [4- (2, 4-dichlorophenoxy) phenoxy ] propionate, N- (3, 4-dichlorophenyl) -N ', N' -dimethylurea.
Coatings according to other embodiments of the invention, the anti-algae compound: the mass ratio of the porous carrier is (3-10): 1.
according to other embodiments of the coating material, the auxiliary agent comprises at least one of a thickener, a defoamer, an anti-settling agent and a dispersant.
According to other embodiments of the present invention, the thickener includes, but is not limited to, sodium polyacrylate in an amount of 0.1 to 1 wt%, or fumed silica in an amount of 0.5 to 1%.
In other embodiments of the coating according to the present invention, the defoamer comprises, but is not limited to, tributyl phosphate, added in an amount of 0.1 to 1 wt%.
According to other embodiments of the present invention, the anti-settling agent comprises, but is not limited to, organic montmorillonite, and is added in an amount of 0.1 to 1 wt%.
According to other embodiments of the present invention, the dispersant includes, but is not limited to, an aqueous dispersant, and is added in an amount of 0.1 to 1 wt%.
According to the paint of other embodiments of the invention, the composite nano-silver material prepared in the above way is uniformly mixed with the anti-algae agent and the silicate solution, and the zinc powder and the auxiliary agent are added to form the paint under the condition of high-speed stirring.
According to the paint provided by the invention, the nano silver wires with the magnetic metal particles deposited on the surface are added into the paint, and the nano silver wires can be oriented and arranged at a certain angle with the coating under the action of an external electric field, so that the problem of insufficient antibacterial durability caused by easy dissolution of common nano silver particles as an antibacterial agent is solved. Meanwhile, the high-length-diameter ratio nano silver wire and the zinc powder in the coating form a high-efficiency conductive network, the cathode protection effect of the zinc-rich anticorrosive coating is improved, the addition amount of the zinc powder is reduced, and the anticorrosion life of the anticorrosive coating is prolonged. The anti-algae agent formed by the anti-algae compound and the porous carrier load achieves the fixing and slow-release effects of the anti-algae agent by utilizing the characteristics of the porous structure of the carrier, prolongs the anti-algae performance of the coating and prolongs the corrosion-resistant life. The addition of the raw materials such as the magnetic nano silver wire, the anti-algae agent, the flaky zinc powder and the granular zinc powder ensures that the formed coating is compact and has fewer pores. On one hand, the coating is multifunctional due to the addition of the magnetic nano silver wires and the algaecide, and the efficiency of the conductive network in the anticorrosive coating can be improved due to the directionally arranged magnetic nano silver wires. On the other hand, the anti-corrosion network consisting of the flaky zinc powder and the granular zinc powder can prolong the shielding path of the coating to water and oxygen in the environment, and simultaneously increase the release path of the antibacterial agent and the anti-algae agent. The service life of the coating is prolonged by the aid of the synergistic effect of the multiple ways, and the coating is endowed with excellent antibacterial, anti-algae and anti-corrosion properties by means of mutual cooperation of the components, and is particularly suitable for protecting steel members in hot and humid environments.
The invention also provides a preparation method of the coating, which comprises the following steps:
preparing a composite algicide;
preparing an antibacterial agent;
mixing the anti-algae agent, the antibacterial agent and the stable high-modulus silicate solution, and adding the zinc powder and the coating auxiliary agent to form the coating.
According to other embodiments of the present invention, a stable high modulus silicate is prepared by reacting a silicate, a silane coupling agent, and a silicone-acrylic emulsion at a temperature of 30-60 ℃.
According to the preparation method of the coating, the silicate solution is prepared by reacting raw materials including hydroxide of alkali metal, silica sol and water at 40-70 ℃;
wherein, the hydroxide of alkali metal: silica sol: the molar ratio of water is 1: (8-14): (5-10).
In a fourth aspect, an embodiment of the present invention provides a method for using the above coating, including the steps of:
the coating is applied to a substrate and after the coating has formed a film, an electric field is applied perpendicular to the substrate.
The application method provided by the invention adds the nano silver wires with the magnetic metal particles deposited on the surface into the coating, and enables the nano silver wires to be oriented and arranged at a certain angle with the coating under the action of an external electric field, thereby overcoming the problem of insufficient antibacterial durability caused by easy dissolution of common nano silver particles as an antibacterial agent.
According to the application method of the coating according to other embodiments of the present invention, after the film is formed on the surface of the substrate by a coating method such as brushing, spraying, rolling, and the like, an electric field perpendicular to the substrate is applied, and a coating layer in which the magnetic nano silver wires are arranged in a certain direction in the coating layer is obtained.
In a fifth aspect, an embodiment of the present invention provides a coating layer, which is obtained by applying the above-mentioned paint.
According to other embodiments of the coating, the coating is obtained by applying the coating to a substrate by using the method.
In a sixth aspect, an embodiment of the invention provides an article comprising the coating described above.
Articles according to other embodiments of the present invention include a substrate and a coating applied to the substrate.
According to other embodiments of the invention, the substrate is a metal substrate, or a device, apparatus, etc. having a metal substrate. For example, it may be a steel material, or a device or apparatus comprising a steel material.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
This example provides a coating comprising, based on the total mass of the coating, 1.5wt% antimicrobial agent, 1.5wt% anti-algae agent, 30wt% stable high modulus potassium silicate solution, 1.5wt% fumed silica thickener, 0.5wt% montmorillonite anti-settling agent, 0.5wt% dispersant, 0.5wt% defoamer, 48wt% particulate zinc powder, 16wt% flake zinc powder. Wherein the antibacterial agent is a nano silver wire loaded with magnetic iron oxide (ferroferric oxide); the anti-algae agent is diatomite loaded with zinc pyrithione; the modulus of the stable high-modulus potassium silicate solution is 4.5; the granular zinc powder is spherical, and the mesh number is 400-600 meshes; the thickness of the flaky zinc powder is 0.15-0.4 μm, the average grain diameter is 15-25 μm, and the ratio of the diameter to the thickness is 50-70.
The coating is prepared by the following steps:
(1) preparing a silicate solution: taking the molar ratio of 1: 10: 6, mixing and dissolving potassium hydroxide, silica sol and water to obtain a potassium hydroxide solution. Gradually dripping the potassium hydroxide solution into the silica sol under the rapid stirring, and reacting for 1h at the water bath temperature of 50 ℃ to prepare the high-modulus potassium silicate solution with the silicate modulus of 4.5.
(2) Preparation of stable high modulus silicate: according to high modulus potassium laurate solution: silane coupling agent: the mass ratio of the silicone-acrylic emulsion is 1: 0.5: (2-5), weighing the silane coupling agent KH-560 and the silicone-acrylic emulsion, slowly dripping the silane coupling agent KH-560 and the silicone-acrylic emulsion into the high-modulus potassium silicate solution under the stirring condition of 250r/min, reacting at the temperature of 45 ℃ for 1 hour, and preparing the stable high-modulus potassium silicate solution.
(3) Preparing an anti-algae agent: zinc pyrithione with the particle size of 1 mu m is selected as an anti-algae compound, diatomite with the particle size of 5 mu m is selected as a porous carrier, and the loading is carried out according to the following method: 0.5g of the anti-algae compound is weighed out and dissolved in a solvent with the volume ratio of 1: and (1) mechanically stirring the mixed solution of water and ethanol for 30min by ultrasonic strong force. And then 3g of diatomite is weighed and added into the dispersion liquid, strong ultrasonic stirring is continuously carried out for 1-2 hours, then water washing or ethanol washing is carried out, centrifugal vacuum drying is carried out at the speed of 4000-6000 r/min, and the anti-algae agent is obtained.
(4) Preparing an antibacterial agent: FeCl is added3·6H2O and FeSO4·7H2O is added into the mixture in a molar ratio of 1: (1-1.5) preparing into aqueous solution, and stirring and mixing uniformly. Adding 10wt% of nano silver wire aqueous solution into the ferric salt solution according to the mass ratio of 10:100, stirring and mixing uniformly, gradually dropwise adding 5wt% of NaOH solution until the pH value of the mixed solution is 11-12, standing for 3h, performing suction filtration and pure water washing, and performing vacuum drying to obtain the composite nano silver material.
(5) Uniformly mixing 1.5wt% of an antibacterial agent, 1.5wt% of an anti-algae agent and 30wt% of a stable high-modulus potassium silicate solution, stirring at the speed of 1500r/min for 30min, gradually adding 1.5wt% of a fumed silica thickener, 0.5wt% of an anti-settling agent montmorillonite, 0.5wt% of a dispersing agent and 0.5wt% of a defoaming agent during stirring, and finally adding 48wt% of granular zinc powder and 16wt% of flaky zinc powder to obtain the coating.
(6) The prepared coating is coated on a base material in a brushing, spraying or rolling way, and an external magnetic field vertical to the direction of the base material is immediately applied, so that the composite nano silver material in the coating can be arranged at a certain angle with the coating.
Example 2
This example provides a coating, which differs from example 1 in the ratio of the components of the coating and the modulus of the stable high modulus potassium silicate solution, as follows: 1 wt% of antibacterial agent, 1 wt% of anti-algae agent, 31 wt% of stable high-modulus potassium silicate solution, 1.5wt% of fumed silica thickener, 0.5wt% of montmorillonite anti-settling agent, 0.5wt% of dispersing agent, 0.5wt% of defoaming agent, 44 wt% of granular zinc powder and 20 wt% of flaky zinc powder; the modulus of the high-modulus potassium silicate solution was 5.0.
The preparation process is referred to example 1.
Example 3
Comparison of antibacterial and anti-algae properties of the coating
Comparative example 1: a coating comprising, based on the total mass of the coating, 30wt% of a stable high modulus potassium silicate solution, 1.5wt% of an antimicrobial agent, 1.5wt% of an anti-algae agent, 1.5wt% of a fumed silica thickener, 0.5wt% of a montmorillonite anti-settling agent, 0.5wt% of a dispersant, 0.5wt% of a defoamer, 48wt% of a particulate zinc powder, 16wt% of a zinc flake powder; wherein the modulus of the high-modulus potassium silicate solution is 4.5, the antibacterial agent used in the comparative example is nano-silver composite antibacterial powder, illite clay is selected to load an organic antibacterial agent (chitosan quaternary ammonium salt) and an inorganic antibacterial agent (silver nano-particle), the average particle size of the powder is 1-2 mu m, and the anti-algae agent is the same as that of the example.
The preparation process is referred to example 1.
The coatings of examples 1, 2 and comparative example 1 were prepared according to the preparation method of example 1, respectively. The properties of the coating were tested according to the method of table 1, and the test results are shown in table 2. Wherein, the manufacturing process of the test plate is as follows: and spraying a layer of the prepared coating on the surface of the steel plate subjected to sand blasting to enable the thickness of a coating film to reach 50 mu m. The coating film was then tested.
TABLE 1 coating Property test method
TABLE 2 paint property test results
As can be seen from the experimental results of the examples 1-2 and the comparative example 1, the coating adopting the antibacterial agent of the embodiment of the invention has good corrosion resistance, the addition of the magnetic nano silver wire antibacterial agent enables the coating to have good antibacterial effect, the antibacterial durability is greatly improved compared with the traditional nano silver particles, and the service life of the whole coating can be prolonged.
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (1)
1. The method for improving the antibacterial property of the base material is characterized by comprising the following steps: the prepared coating is coated on a substrate by brushing, spraying or rolling, and an external magnetic field vertical to the direction of the substrate is immediately applied, so that the composite nano-silver material in the coating can be arranged at a certain angle with the coating;
the coating comprises 1.5wt% of an antibacterial agent, 1.5wt% of an anti-algae agent, 30wt% of a stable high-modulus potassium silicate solution, 1.5wt% of a fumed silica thickener, 0.5wt% of a montmorillonite anti-settling agent, 0.5wt% of a dispersant, 0.5wt% of a defoaming agent, 48wt% of granular zinc powder and 16wt% of flaky zinc powder based on the total mass of the coating; the antibacterial agent is a nano silver wire loaded with magnetic iron oxide; the anti-algae agent is diatomite loaded with zinc pyrithione; the modulus of the stable high-modulus potassium silicate solution is 4.5; the granular zinc powder is spherical, and the mesh number is 400-600 meshes; the thickness of the flaky zinc powder is 0.15-0.4 μm, the average grain diameter is 15-25 μm, and the ratio of the diameter to the thickness is 50-70;
the coating is prepared by the following steps:
(1) preparing a silicate solution: taking the molar ratio of 1: 10: 6, mixing potassium hydroxide, silica sol and water, and premixing and dissolving the potassium hydroxide and the water to obtain a potassium hydroxide solution; gradually dripping a potassium hydroxide solution into the silica sol under the condition of rapid stirring, and reacting for 1h at the water bath temperature of 50 ℃ to prepare a high-modulus potassium silicate solution with the silicate modulus of 4.5;
(2) preparation of stable high modulus silicate: according to the high modulus potassium silicate solution: silane coupling agent: the mass ratio of the silicone-acrylic emulsion is 1: 0.5: (2-5), weighing a silane coupling agent KH-560 and a silicone acrylic emulsion, slowly dripping the silane coupling agent KH-560 and the silicone acrylic emulsion into the high-modulus potassium silicate solution under the stirring condition of 250r/min, reacting at 45 ℃ for 1 hour, and preparing a stable high-modulus potassium silicate solution;
(3) preparing an anti-algae agent: zinc pyrithione with the particle size of 1 mu m is selected as an anti-algae compound, diatomite with the particle size of 5 mu m is selected as a porous carrier, and the loading is carried out according to the following method: 0.5g of the anti-algae compound is weighed out and dissolved in a solvent with the volume ratio of 1: (1-2) mechanically stirring the mixed solution of water and ethanol for 30min by ultrasonic strong force; then weighing 3g of diatomite, adding the diatomite into the dispersion liquid, continuing to stir for 1-2h by strong ultrasonic waves, then washing with water or ethanol, and centrifugally drying in vacuum at 4000-6000 r/min to obtain the anti-algae agent;
(4) preparing an antibacterial agent: FeCl is added3·6H2O and FeSO4·7H2O is added into the mixture in a molar ratio of 1: (1-1.5) preparing into aqueous solution, and uniformly stirring and mixing; adding 10wt% of nano silver wire aqueous solution into the ferric salt solution according to the mass ratio of 10:100, stirring and mixing uniformly, and gradually dropwise adding 5wt% of NaOH solution until the pH value of the mixed solution reaches11-12, standing for 3h, washing with suction filtration pure water, and drying in vacuum to obtain a composite nano silver material;
(5) 1.5wt% of an antibacterial agent, 1.5wt% of an anti-algae agent and 30wt% of a stable high-modulus potassium silicate solution are uniformly mixed, the mixture is stirred for 30min at the speed of 1500r/min, 1.5wt% of a gas-phase silicon dioxide thickening agent, 0.5wt% of an anti-settling agent montmorillonite, 0.5wt% of a dispersing agent and 0.5wt% of a defoaming agent are gradually added during stirring, and finally 48wt% of granular zinc powder and 16wt% of flaky zinc powder are added to obtain the coating.
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| CN103289453A (en) * | 2013-07-08 | 2013-09-11 | 华夏贝能（北京）生态科技有限公司 | Anti-bacteria deodorizing inorganic functional coating and preparation method thereof |
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